CA1225310A - Process for phosphating metals - Google Patents
Process for phosphating metalsInfo
- Publication number
- CA1225310A CA1225310A CA000452666A CA452666A CA1225310A CA 1225310 A CA1225310 A CA 1225310A CA 000452666 A CA000452666 A CA 000452666A CA 452666 A CA452666 A CA 452666A CA 1225310 A CA1225310 A CA 1225310A
- Authority
- CA
- Canada
- Prior art keywords
- phosphating
- seconds
- zinc
- phosphate
- dipping
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
In a process for phosphating composite metals containing steel and zinc surfaces using phosphating solutions based on zinc phosphate by the dipping process, in order to achieve satisfactory formation of the phosphate layer, the composite metals are subjected, to preliminary dipping for a maximum of 30 seconds in a phosphating solution based on zinc phosphate in order to initiate the formation of the phosphate layer, and are then conveyed to the main dip-phosphating zone.
It is advantageous to spray the composite metals with a phosphating solution based on zinc phosphate while they are being conveyed from the preliminary to the main dip-phos-phating zone, and it is advisable to limit the duration of the conveying and thus of the spraying treatment to a maximum of 30 seconds.
In a process for phosphating composite metals containing steel and zinc surfaces using phosphating solutions based on zinc phosphate by the dipping process, in order to achieve satisfactory formation of the phosphate layer, the composite metals are subjected, to preliminary dipping for a maximum of 30 seconds in a phosphating solution based on zinc phosphate in order to initiate the formation of the phosphate layer, and are then conveyed to the main dip-phosphating zone.
It is advantageous to spray the composite metals with a phosphating solution based on zinc phosphate while they are being conveyed from the preliminary to the main dip-phos-phating zone, and it is advisable to limit the duration of the conveying and thus of the spraying treatment to a maximum of 30 seconds.
Description
3~0 Case: P30,031 PROCESS FOR PHOSPHATING_METALS
Background of the Invention The invention relates to a process for phosphating composite metals containing steel and zinc surfaces and having cavities, using phosphating solutions based on zinc phosphate, by the dipping process.
Steel sheets having an improved surface, in particular galvanized steel sheets, composite metals as they are called, are becoming increasingly important in industrial mass production.
Composite metals of this type are obtained by joining steel sheets and galvanized steel sheets and also by partially galvanizing steel sheets. Before painting, especially application of paint by elect trodeposition, phosphating with solutions based on zinc phosphate in order to improve corrosion resistance and adhesion of paint is necessary, just as it is for components containing only steel or zinc surfaces.
The special feature in the phosphating of composite metals containing zinc and steel surfaces is the fact that, when contact takes place with the phosphating solution, particularly in dip treatment, an electrochemical cell is formed, with the zinc surface as the anode and the steel surface as the cathode.
As a result, in the immediate neighborhood of the zinc surface, the cathodic current density on the steel surface is so high that the phosphating process is adversely affected (W. Bausch, "Chemische Oberflachenbehandlung vow verzinktem undo zinkstaub-lackiertem Stahl fur die kathodische Elektrotauchlackierung"
, I
("The chemical surface treatment of galvanized steel and steel painted with zinc dust for the application of paint by cathodic electrode position") Industries Lackierbetrieb 49 (1981), pages 413 et seq.).
- 5 Thus, in phosphating by dipping, the formation of a phosphate layer is interfered with to such an extent that, depending on the phosphating process, a strip about 5 to 10 mm wide, carrying a very translucent and only incompletely formed phosphate layer, is formed on the steel side.
Spraying and spraying/dipping processes present fewer difficulties because the formation of an electrochemical cell is incomplete. The strip mentioned above is generally not formed, but the whole phosphate layer is frequently streaky and has an adverse effect on the paint system subsequently applied.
Specifically for the treatment of composite metals of the type mentioned above, it is known to carry out treatment, first by dipping and then by spraying, using phosphating solutions containing 0.5 to 1.5 g/liter of zinc, 5 to 30 g/liter of phosphate ions, 0.6 to 3 g/liter of manganese ions and customary accelerators (European Laid-Open Specification 60,716). The dipping treatment should in this case be at least 15 seconds, advantageously 0.5 to
Background of the Invention The invention relates to a process for phosphating composite metals containing steel and zinc surfaces and having cavities, using phosphating solutions based on zinc phosphate, by the dipping process.
Steel sheets having an improved surface, in particular galvanized steel sheets, composite metals as they are called, are becoming increasingly important in industrial mass production.
Composite metals of this type are obtained by joining steel sheets and galvanized steel sheets and also by partially galvanizing steel sheets. Before painting, especially application of paint by elect trodeposition, phosphating with solutions based on zinc phosphate in order to improve corrosion resistance and adhesion of paint is necessary, just as it is for components containing only steel or zinc surfaces.
The special feature in the phosphating of composite metals containing zinc and steel surfaces is the fact that, when contact takes place with the phosphating solution, particularly in dip treatment, an electrochemical cell is formed, with the zinc surface as the anode and the steel surface as the cathode.
As a result, in the immediate neighborhood of the zinc surface, the cathodic current density on the steel surface is so high that the phosphating process is adversely affected (W. Bausch, "Chemische Oberflachenbehandlung vow verzinktem undo zinkstaub-lackiertem Stahl fur die kathodische Elektrotauchlackierung"
, I
("The chemical surface treatment of galvanized steel and steel painted with zinc dust for the application of paint by cathodic electrode position") Industries Lackierbetrieb 49 (1981), pages 413 et seq.).
- 5 Thus, in phosphating by dipping, the formation of a phosphate layer is interfered with to such an extent that, depending on the phosphating process, a strip about 5 to 10 mm wide, carrying a very translucent and only incompletely formed phosphate layer, is formed on the steel side.
Spraying and spraying/dipping processes present fewer difficulties because the formation of an electrochemical cell is incomplete. The strip mentioned above is generally not formed, but the whole phosphate layer is frequently streaky and has an adverse effect on the paint system subsequently applied.
Specifically for the treatment of composite metals of the type mentioned above, it is known to carry out treatment, first by dipping and then by spraying, using phosphating solutions containing 0.5 to 1.5 g/liter of zinc, 5 to 30 g/liter of phosphate ions, 0.6 to 3 g/liter of manganese ions and customary accelerators (European Laid-Open Specification 60,716). The dipping treatment should in this case be at least 15 seconds, advantageously 0.5 to
2 minutes, and the spraying treatment should be at least 2 seconds, advantageously 5 to 45 seconds. Even using this process, come posit metals containing cavities cannot be phosphate in a satisfactory manner.
The object of the invention is to provide a process, for phosphating composite metals containing steel and zinc surfaces and having cavities, which does not have the disadvantages of the processes mentioned above, but results in a satisfactory, continuous it phosphate layer - without additional outlay on the process.
Summary of the Invention _ This object is achieved by modifying, in accordance with the invention, the process of the type mentioned initially in such a way that the composite metals are dipped beforehand, into a phosphating solution based on zinc phosphate for not more than 30 seconds in order to initiate the formation of the phosphate layer, and are then conveyed to the zone of actual dip-phosphating.
lo Detailed Description of the Invention .
Any desired phosphating solutions based on zinc pros-plate can be employed for carrying out the phosphating process.
They can form part of either the so-called low-zinc technology or of the standard zinc technology. This means that the combo-site metals can be brought in contact with a phosphating solution in which the weight ratio of Zen to P205 has been adjusted to l : (8 to 85), or with a phosphating solution in which the weight ratio of Zen to P205 has been adjusted to l : (0.3 to 7).
In the first case, phosphate layers having a high proportion of phosphophyllite to hopeite are formed on the steel.
These coatings are particularly suitable, because of their ox-silent corrosion resistance, as a preparatory treatment for painting, the best protective properties being achieved in con-junction with the application of paint by cathodic electrodepo-session.
In the second case, the result is phosphating processes which are distinguished by a higher phosphating speed compared So with the low-zinc processes. The phosphate layers produced by means ox them have good properties for a wide spectrum of uses in the fields of corrosion resistance and cold deformation without machining.
The aqueous acid solutions, to be used within the scope of the invention, based on zinc phosphate contain primary zinc phosphate and a certain amount, adjusted to suit the par-titular bath concentration, mode of use and bath temperature, of free acid. The pi of the baths is, for instance, between 2.0 and 3.9, depending on the process conditions.
The baths can also contain further cations which are known in the technology of phosphating, for example Nix Co, Cut My, Cay My, Fe, Nay K, H, NH4 and others. In order to adjust the acidity and to achieve special technical effects, it can be necessary or desirable to use concomitantly further anions other than phosphate, for example N03, C103, Of, SO, F, BF4, Sift, citrate, tart rate and others.
The contact time for the phosphating solution used in the final dip treatment is usually between 1 and 10 minutes.
The temperature of the phosphating solution is about 30 to 60C.
The lower the temperature, the longer, usually, is the contact time.
An advantageous embodiment of the invention consists in spraying the composite metals with a phosphating solution based on zinc phosphate while they are being conveyed to the zone of dip-phosphating, and, furthermore, limiting the conveying to the zone of dip-phosphating, and thus the spraying treatment, to a maximum of 30 seconds.
53~
This procedure has the advantage -that, during the transfer of the metal surface to the final dip-treatment, fresh phosphating solution is available for forming an unvarying film of liquid on the metal surface. This prevents liquid films of different thicknesses being present on the metal surface as a result of the liquid draining off. The advantage of the above-mentioned measure manifests itself particularly in the formation of uniform phosphate layers.
In other respects, the measures customary in connect lion with phosphating processes are also applicable in the case of the present process. These are, in particular, decreasing and rust removal, preliminary rinsing to activate the formation of the phosphate layer, and after-treatment with re-rinsing solutions based on Or (VI) and/or Or (III) etc., or with impreg-noting agents, such as rustproofing oils or waxes and synthetic resins.
When phosphating solutions based on zinc phosphate are mentioned in the above statements in connection with the actual dip-treatment, the brief dipping prior to transfer and the spraying treatment while the composite metals are conveyed to the dip-treatment, these solutions are usually solutions of essentially the same composition. Certain deviations are, as a rule, mainly the consequence of varying exhaustion of the phosphating solution and of the increased precipitation of iron caused by the action of atmospheric oxygen in the spraying treat-mint.
The invention is exemplified and illustrated in more detail on the basis of the examples.
53~) Examples Composite metals composed of steel sheet and galvanized steel sheet were treated by the following procedures.
l) Preliminary cleaning using an alkaline cleaner at 60C, spraying for 4 minutes.
2) Main cleaning using the same cleaner at 80C;
dipping for 9.5 minutes.
The object of the invention is to provide a process, for phosphating composite metals containing steel and zinc surfaces and having cavities, which does not have the disadvantages of the processes mentioned above, but results in a satisfactory, continuous it phosphate layer - without additional outlay on the process.
Summary of the Invention _ This object is achieved by modifying, in accordance with the invention, the process of the type mentioned initially in such a way that the composite metals are dipped beforehand, into a phosphating solution based on zinc phosphate for not more than 30 seconds in order to initiate the formation of the phosphate layer, and are then conveyed to the zone of actual dip-phosphating.
lo Detailed Description of the Invention .
Any desired phosphating solutions based on zinc pros-plate can be employed for carrying out the phosphating process.
They can form part of either the so-called low-zinc technology or of the standard zinc technology. This means that the combo-site metals can be brought in contact with a phosphating solution in which the weight ratio of Zen to P205 has been adjusted to l : (8 to 85), or with a phosphating solution in which the weight ratio of Zen to P205 has been adjusted to l : (0.3 to 7).
In the first case, phosphate layers having a high proportion of phosphophyllite to hopeite are formed on the steel.
These coatings are particularly suitable, because of their ox-silent corrosion resistance, as a preparatory treatment for painting, the best protective properties being achieved in con-junction with the application of paint by cathodic electrodepo-session.
In the second case, the result is phosphating processes which are distinguished by a higher phosphating speed compared So with the low-zinc processes. The phosphate layers produced by means ox them have good properties for a wide spectrum of uses in the fields of corrosion resistance and cold deformation without machining.
The aqueous acid solutions, to be used within the scope of the invention, based on zinc phosphate contain primary zinc phosphate and a certain amount, adjusted to suit the par-titular bath concentration, mode of use and bath temperature, of free acid. The pi of the baths is, for instance, between 2.0 and 3.9, depending on the process conditions.
The baths can also contain further cations which are known in the technology of phosphating, for example Nix Co, Cut My, Cay My, Fe, Nay K, H, NH4 and others. In order to adjust the acidity and to achieve special technical effects, it can be necessary or desirable to use concomitantly further anions other than phosphate, for example N03, C103, Of, SO, F, BF4, Sift, citrate, tart rate and others.
The contact time for the phosphating solution used in the final dip treatment is usually between 1 and 10 minutes.
The temperature of the phosphating solution is about 30 to 60C.
The lower the temperature, the longer, usually, is the contact time.
An advantageous embodiment of the invention consists in spraying the composite metals with a phosphating solution based on zinc phosphate while they are being conveyed to the zone of dip-phosphating, and, furthermore, limiting the conveying to the zone of dip-phosphating, and thus the spraying treatment, to a maximum of 30 seconds.
53~
This procedure has the advantage -that, during the transfer of the metal surface to the final dip-treatment, fresh phosphating solution is available for forming an unvarying film of liquid on the metal surface. This prevents liquid films of different thicknesses being present on the metal surface as a result of the liquid draining off. The advantage of the above-mentioned measure manifests itself particularly in the formation of uniform phosphate layers.
In other respects, the measures customary in connect lion with phosphating processes are also applicable in the case of the present process. These are, in particular, decreasing and rust removal, preliminary rinsing to activate the formation of the phosphate layer, and after-treatment with re-rinsing solutions based on Or (VI) and/or Or (III) etc., or with impreg-noting agents, such as rustproofing oils or waxes and synthetic resins.
When phosphating solutions based on zinc phosphate are mentioned in the above statements in connection with the actual dip-treatment, the brief dipping prior to transfer and the spraying treatment while the composite metals are conveyed to the dip-treatment, these solutions are usually solutions of essentially the same composition. Certain deviations are, as a rule, mainly the consequence of varying exhaustion of the phosphating solution and of the increased precipitation of iron caused by the action of atmospheric oxygen in the spraying treat-mint.
The invention is exemplified and illustrated in more detail on the basis of the examples.
53~) Examples Composite metals composed of steel sheet and galvanized steel sheet were treated by the following procedures.
l) Preliminary cleaning using an alkaline cleaner at 60C, spraying for 4 minutes.
2) Main cleaning using the same cleaner at 80C;
dipping for 9.5 minutes.
3) Rinsing with cold water by dipping.
4) Activation by means of a titanium phosphate solution for l minute by dipping.
5) Phosphating at 60C using a solution containing:
1.5 g/liter of Zen 0.4 g/liter of No 22.5 g/liter of P205 and 0.14 g/liter of Nina, and containing 1.6 to 1.7 points of free acid, 36 points of total acid and also an S-value acid of 0.05 to 0.06.
1.5 g/liter of Zen 0.4 g/liter of No 22.5 g/liter of P205 and 0.14 g/liter of Nina, and containing 1.6 to 1.7 points of free acid, 36 points of total acid and also an S-value acid of 0.05 to 0.06.
6) Rinsing with cold water by dipping.
7) Re-rinsing with a CrIII/CrVI solution by dipping.
8) Drying in an oven for 15 minutes.
Under identical conditions in respect of stages 1 to 4 and 6 to 8, the dipping and spraying times within the pros-plating stage were varied in accordance with the entries in the table below.
., .
I
Phosphating Layer Formation on Steel Preliminary Preliminary Dipping at the border on the Dippin~Spravinq with the zinc surface ..~
- --- 4 minutes translucent continuous 2. --- 10 seconds 4 minutes continuous streaky 3. --- 20 seconds 4 minutes continuous streaky 4. --- 30 seconds 4 minutes continuous streaky 5.25 seconds seconds 4 minutes continuous continuous 6. 25 seconds 20 seconds 4 minutes continuous continuous 7. 25 seconds 30 seconds 4 minutes continuous continuous 8. 50 seconds 10 seconds 4 minutes translucent continuous
Under identical conditions in respect of stages 1 to 4 and 6 to 8, the dipping and spraying times within the pros-plating stage were varied in accordance with the entries in the table below.
., .
I
Phosphating Layer Formation on Steel Preliminary Preliminary Dipping at the border on the Dippin~Spravinq with the zinc surface ..~
- --- 4 minutes translucent continuous 2. --- 10 seconds 4 minutes continuous streaky 3. --- 20 seconds 4 minutes continuous streaky 4. --- 30 seconds 4 minutes continuous streaky 5.25 seconds seconds 4 minutes continuous continuous 6. 25 seconds 20 seconds 4 minutes continuous continuous 7. 25 seconds 30 seconds 4 minutes continuous continuous 8. 50 seconds 10 seconds 4 minutes translucent continuous
9. 50 seconds 20 seconds 4 minutes translucent continuous
10.50 seconds seconds 4 minutes translucent continuous
11.70 seconds seconds 4 minutes translucent continuous
12.70 seconds seconds 4 minutes translucent continuous
13.70 seconds seconds 4 minutes translucent continuous The tests show that, with dip phosphating (1) alone, a strip having only an incompletely formed and therefore trays-lucent phosphate layer is obtained at the boundary with the zinc surface. Although this strip is satisfactorily phosphate and carries a continuous phosphate layer if a spraying treatment is carried out beforehand (2 to 4), the whole surface of the steel is covered with streaky phosphate layers.
With an additional preliminary dipping corresponding -to the process according to the invention (5 to 7), the formation of the phosphate layer is satisfactory both near to the zinc sun-face and on the whole surface of the steel.
Sue Although the phosphate layer on the surface of the steel remains continuous with a longer preliminary dipping, it is incompletely formed and is translucent within the zone of action of the zinc surface.
With an additional preliminary dipping corresponding -to the process according to the invention (5 to 7), the formation of the phosphate layer is satisfactory both near to the zinc sun-face and on the whole surface of the steel.
Sue Although the phosphate layer on the surface of the steel remains continuous with a longer preliminary dipping, it is incompletely formed and is translucent within the zone of action of the zinc surface.
Claims (3)
1. A process for phosphating composite metal articles containing steel and zinc surfaces, using phosphating solutions based on zinc phosphate by the dipping process, which comprises subjecting the composite metals, to a preliminary dipping of not more than 30 seconds in a phosphating solution based on zinc phosphate, and then conveying the articles to the main dip-phosphating zone.
2. The process of Claim 1, wherein the composite metal articles are sprayed with a phosphating solution based on zinc phosphate while they are being conveyed from the preliminary dipping zone to the main dip-phosphating zone.
3. The process of Claim 2, wherein the conveying time from the preliminary to the main dip-phosphating zone is limited to a maximum of 30 seconds.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833315086 DE3315086A1 (en) | 1983-04-26 | 1983-04-26 | METHOD FOR PHOSPHATING COMPOSITE METALS |
| DEP3315086.9 | 1983-04-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1225310A true CA1225310A (en) | 1987-08-11 |
Family
ID=6197396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000452666A Expired CA1225310A (en) | 1983-04-26 | 1984-04-24 | Process for phosphating metals |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US4559087A (en) |
| EP (1) | EP0127204B1 (en) |
| JP (1) | JPS59205482A (en) |
| AU (1) | AU566551B2 (en) |
| BR (1) | BR8401938A (en) |
| CA (1) | CA1225310A (en) |
| DE (2) | DE3315086A1 (en) |
| ES (1) | ES531203A0 (en) |
| GB (1) | GB2138844B (en) |
| NZ (1) | NZ207947A (en) |
| PT (1) | PT78409B (en) |
| ZA (1) | ZA843104B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5268041A (en) * | 1990-04-27 | 1993-12-07 | Metallgesellschaft Ag | Process for phosphating metal surfaces |
| EP0653502A3 (en) * | 1993-11-11 | 1995-08-09 | Nihon Parkerizing | Zinc-containing metal-plated composite steel article and method of producing the same. |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE452007A (en) * | 1942-05-05 | |||
| US2552874A (en) * | 1950-05-01 | 1951-05-15 | American Chem Paint Co | Method of phosphatizing ferriferous surfaces |
| BE635605A (en) * | 1962-08-01 | |||
| GB1084017A (en) * | 1963-09-30 | 1967-09-20 | Jawata Iron & Steel Co Ltd | Pretreating process for phosphate-treating steel sheets or plated steel sheets |
| JPS4824135B1 (en) * | 1968-12-20 | 1973-07-19 | ||
| ZA722987B (en) * | 1971-05-10 | 1973-02-28 | Craig S Investments Pty Ltd | Rust proofing process |
| DE2207047A1 (en) * | 1972-02-15 | 1973-08-30 | Metallgesellschaft Ag | PROCESS FOR THE PREPARATION OF STEEL PIECES FOR CHIPLESS COLD FORMING |
| SE406940B (en) * | 1974-04-13 | 1979-03-05 | Collardin Gmbh Gerhard | PROCEDURE FOR PREPARING PHOSPHATE COATINGS BY THE IRON AND STEEL SPRAYING METHOD |
| JPS5811513B2 (en) * | 1979-02-13 | 1983-03-03 | 日本ペイント株式会社 | How to protect metal surfaces |
| JPS57152472A (en) * | 1981-03-16 | 1982-09-20 | Nippon Paint Co Ltd | Phosphating method for metallic surface for cation type electrodeposition painting |
| US4400416A (en) * | 1981-05-19 | 1983-08-23 | Toyota Jidosha Kogyo Kabushiki Kaisha | Method of surface treatment and an apparatus used in said surface treatment |
-
1983
- 1983-04-26 DE DE19833315086 patent/DE3315086A1/en not_active Withdrawn
-
1984
- 1984-03-20 EP EP84200398A patent/EP0127204B1/en not_active Expired
- 1984-03-20 DE DE8484200398T patent/DE3468702D1/en not_active Expired
- 1984-03-30 ES ES531203A patent/ES531203A0/en active Granted
- 1984-04-11 PT PT78409A patent/PT78409B/en not_active IP Right Cessation
- 1984-04-17 US US06/600,587 patent/US4559087A/en not_active Expired - Fee Related
- 1984-04-24 CA CA000452666A patent/CA1225310A/en not_active Expired
- 1984-04-25 BR BR8401938A patent/BR8401938A/en unknown
- 1984-04-25 JP JP59083586A patent/JPS59205482A/en active Pending
- 1984-04-26 GB GB08410726A patent/GB2138844B/en not_active Expired
- 1984-04-26 ZA ZA843104A patent/ZA843104B/en unknown
- 1984-04-26 AU AU27280/84A patent/AU566551B2/en not_active Ceased
- 1984-04-26 NZ NZ207947A patent/NZ207947A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE3468702D1 (en) | 1988-02-18 |
| AU566551B2 (en) | 1987-10-22 |
| NZ207947A (en) | 1987-09-30 |
| EP0127204A1 (en) | 1984-12-05 |
| DE3315086A1 (en) | 1984-10-31 |
| ZA843104B (en) | 1984-11-28 |
| PT78409A (en) | 1984-05-01 |
| US4559087A (en) | 1985-12-17 |
| GB8410726D0 (en) | 1984-05-31 |
| GB2138844A (en) | 1984-10-31 |
| EP0127204B1 (en) | 1988-01-13 |
| PT78409B (en) | 1986-05-27 |
| AU2728084A (en) | 1984-11-01 |
| ES8501450A1 (en) | 1984-12-01 |
| BR8401938A (en) | 1984-12-04 |
| JPS59205482A (en) | 1984-11-21 |
| ES531203A0 (en) | 1984-12-01 |
| GB2138844B (en) | 1986-06-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |